Catalysts comprising a zirconia and gallium oxide component for production of c2 to c4 olefins

ABSTRACT

A process for preparing C2 to C4 olefins includes introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor. The feed stream is converted into a product stream including C2 to C4 olefins in the reaction zone in the presence of the hybrid catalyst. The hybrid catalyst includes a metal oxide catalyst component comprising gallium oxide and phase pure zirconia, and a microporous catalyst component.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/785,828 filed on Dec. 28, 2018, the entire disclosure of which ishereby incorporated by reference.

BACKGROUND Field

The present specification generally relates to catalysts thatefficiently convert various carbon-containing streams to C₂ to C₄olefins. In particular, the present specification relates to preparationof hybrid catalysts and application of process methods to achieve a highconversion of synthesis gas feeds resulting in good conversion of carbonand high yield of desired products. The synthesis gas comprises hydrogengas and a carbon-containing gas selected from the group consisting ofcarbon monoxide, carbon dioxide, and mixtures thereof. A hybrid catalystgenerally comprises a combination of a metal oxide component and amicroporous catalyst component that operate in tandem.

Technical Background

For a number of industrial applications, olefins are used, or arestarting materials used, to produce plastics, fuels, and variousdownstream chemicals. Such olefins include C₂ to C₄ materials, such asethylene, propylene, and butylenes (also commonly referred to as ethene,propene and butenes, respectively). A variety of processes for producingthese lower olefins have been developed, including petroleum crackingand various synthetic processes.

Synthetic processes for converting feed carbon to desired products, suchas olefins, are known. Some of these synthetic processes begin with useof a hybrid catalyst. Different types of catalysts have also beenexplored, as well as different kinds of feed streams and proportions offeed stream components. However, many of these synthetic processes havelow carbon conversion and much of the feed carbon either (1) does notget converted and exits the process in the same form as the feed carbon;(2) is converted to CO₂; or (3) these synthetic processes have lowstability over time and the catalyst rapidly loses its activity forcarbon conversion to desirable products. For example, many syntheticprocesses tend to have increased methane production—and, thus, decreasedC₂ to C₄ olefin production—over time.

Accordingly, a need exists for processes and catalytic systems that havea high conversion of feed carbon to desired products, such as, forexample, C₂ to C₄ olefins in combination with a high on stream stabilityof the catalyst.

SUMMARY

According to one embodiment, a process for preparing C₂ to C₄ olefinscomprises: introducing a feed stream comprising hydrogen gas and acarbon-containing gas selected from the group consisting of carbonmonoxide, carbon dioxide, and mixtures thereof into a reaction zone of areactor; and converting the feed stream into a product stream comprisingC₂ to C₄ olefins in the reaction zone in the presence of the hybridcatalyst, the hybrid catalyst comprising: a metal oxide catalystcomponent comprising gallium oxide and phase pure zirconia; and amicroporous catalyst component.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing theembodiments described herein, including the detailed description whichfollows and the claims.

It is to be understood that both the foregoing general description andthe following detailed description describe various embodiments and areintended to provide an overview or framework for understanding thenature and character of the claimed subject matter.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments of hybrid catalystsand methods using the hybrid catalyst to prepare C₂ to C₄ olefins. Inone embodiment, a process for preparing C₂ to C₄ olefins comprises:introducing a feed stream comprising hydrogen gas and acarbon-containing gas selected from the group consisting of carbonmonoxide, carbon dioxide, and mixtures thereof into a reaction zone of areactor; and converting the feed stream into a product stream comprisingC₂ to C₄ olefins in the reaction zone in the presence of the hybridcatalyst, the hybrid catalyst comprising: a metal oxide catalystcomponent comprising gallium oxide and phase pure zirconia; and amicroporous catalyst component.

The use of hybrid catalysts to convert feed streams comprising carbon todesired products, such as, for example, C₂ to C₄ olefins, is known.However, many known hybrid catalysts are inefficient, because theyexhibit a low feed carbon conversion and/or deactivate quickly as theyare used, such as, for example, by having an increase in methaneproduction, which leads to a low olefin yield and low stability for agiven set of operating conditions over a given amount of time. Incontrast, hybrid catalysts disclosed and described herein exhibit a highand steady yield of C₂ to C₄ olefins, even as the catalyst time onstream increases. The composition of such hybrid catalysts used inembodiments is discussed below.

As a summary, hybrid catalysts closely couple independent reactions oneach of the two independent catalysts. In the first step, a feed streamcomprising hydrogen gas (H₂) and at least one of carbon monoxide (CO),carbon dioxide (CO₂), or a mixture of CO and CO₂, such as, for example,syngas, is converted into an intermediate(s) such as oxygenatedhydrocarbons. In the subsequent step, these intermediates are convertedinto hydrocarbons (mostly short chain hydrocarbons, such as, for exampleC₂ to C₄ olefins). The continued formation and consumption of theintermediate oxygenates formed in the first step by the reactions of thesecond step ensures that there is no thermodynamic limit on conversions.With a careful selection of the components to the hybrid catalytic bed,high conversions of the syngas feed can be achieved.

Hybrid catalyst systems comprise a metal oxide catalyst component, whichconverts the feed stream to oxygenated hydrocarbons, and a microporouscatalyst component (such as, for example, a silicoaluminophosphate orSAPO-type molecular sieve component), which converts the oxygenatedhydrocarbons to hydrocarbons. Known hybrid catalyst systems based onchromium-zinc mixed metal oxide catalyst generally exhibit a trade-offbetween initial yield of C₂ to C₄ olefins and sustained yield of C₂ toC₄ olefins as the catalyst time on stream increases (also referred to asstability). There is accordingly a need for a metal oxide catalystcomponent that results in a high initial yield as well as a highstability when combined with a microporous catalyst component in ahybrid catalyst process. It should be understood that, as used herein,the “metal oxide catalyst component” includes metals in variousoxidation states. In some embodiments, the metal oxide catalystcomponent may comprise more than one metal oxide and individual metaloxides within the metal oxide catalyst component may have differentoxidation states. Thus, the metal oxide catalyst component is notlimited to comprising metal oxides with homogenous oxidation states.

Embodiments of hybrid catalysts and systems for using hybrid catalystsdisclosed herein comprise a metal oxide catalyst component comprising:(1) gallium (Ga), and (2) phase pure zirconia (ZrO₂). In someembodiments, the phase pure zirconia may be crystalline, and in someembodiments, the phase pure zirconia may be monoclinic crystalline phasepure zirconia. The metal oxide catalyst component is combined with amicroporous catalyst component. The microporous catalyst component is,according to some embodiments, an 8-MR microporous catalyst component,such as, for example, SAPO-34 molecular sieve.

Metal oxide catalyst components for use in a hybrid catalyst accordingto embodiments will now be described. As referred to above, metalscommonly used as constituents of the metal oxide catalyst component ofsome hybrid catalysts include combinations of zinc (Zn) and chromium(Cr). However, catalysts comprising zinc and chromium, which are knownas high temperature methanol synthesis catalysts, do not have acombination of good olefin yield and good stability when kept on streamfor an extended period of time. Although other metal combinations havebeen used, zinc and chromium have long been thought to be the mostefficient metal oxide components for producing lower olefins, such as C₂to C₄ olefins.

Gallium oxide (gallia, Ga₂O₃) is a very capable promoter formethanol-forming catalysts that are based on palladium, copper ornickel. In such functions, it is believed that upon reduction in thepresence of hydrogen gallium oxide forms sub-oxides and surfacehydrides. Eventually, the reduction process may lead to alloying of Gametal with the active catalyst component (Pd, Cu or Ni) creating abetter performing intermetallic phase such (e.g., Pd—Ga). In contrast,gallium oxides and supported gallium oxides show very poor performancein conversion of syngas. Further, bulk neat gallia used as a metal oxidecomponent of a hybrid catalyst generally yields a high percentage ofparaffins. However, it was unexpectedly found that when gallia wascombined with a phase pure zirconia this combination promoted both thehigh olefin yield and high process stability of the hybrid catalyst.

As used herein, the zirconia used in embodiments disclosed and describedherein in the metal oxide catalyst component of the hybrid catalyst is“phase pure zirconia”, which is defined herein as zirconia to which noother materials have intentionally been added during formation. Thus,“phase pure zirconia” includes zirconia with small amounts of componentsother than zirconium (including oxides other than zirconia) that areunintentionally present in the zirconia as a natural part of thezirconia formation process, such as, for example, hafnium (Hf).Accordingly, as used herein “zirconia” and “phase pure zirconia” areused interchangeably unless specifically indicated otherwise.

Without being bound by any particular theory, it is believed that thehigh surface area of zirconia allows the gallium oxide catalyst actingas part of hybrid catalyst to convert carbon-containing components to C₂to C₄ olefins. It is believed that the gallium oxide and the zirconiaoxide help to activate one another, which results in improved yield forC₂ to C₄ olefins.

Surprisingly, along the high activity and high selectivity of the uniquecombination of Ga/ZrO₂ component used to prepare hybrid catalysts with amolecular sieve, it has been found that such hybrid catalysts comprisinggallium oxide and zirconia as its metal oxide component have improvedstability in extended process times. It was also found, in embodiments,that crystalline zirconia is a particularly effective carrier forgallium oxide. Moreover, in some embodiments, it was found thatmonoclinic zirconia is a particularly good carrier for gallium oxidethat provides combined very high activity without compromising theselectivity for C₂ to C₄ olefins.

In embodiments disclosed herein, the composition of the metal oxidecatalyst component is designated by a weight percentage of the galliummetal to the pure zirconia (accounting for ZrO₂ stoichiometry). In oneor more embodiments, the composition of the metal oxide catalystcomponent is designated by weight of gallium per 100 grams (g) ofzirconia. According to embodiments, the metal oxide catalyst componentcomprises from greater than 0.0 g gallium to 30.0 g gallium per 100 g ofzirconia, such as 5.0 g gallium to 30.0 g gallium per 100 g of zirconia,10.0 g gallium to 30.0 g gallium per 100 g of zirconia, 15.0 g galliumto 30.0 g gallium per 100 g of zirconia, 20.0 g gallium to 30.0 ggallium per 100 g of zirconia, or 25.0 g gallium to 30.0 g gallium per100 g of zirconia. In some embodiments, the metal oxide catalystcomponent comprises from greater than 0.0 g gallium to 25.0 g galliumper 100 g of zirconia, such as from greater than 0.0 g gallium to 20.0 ggallium per 100 g of zirconia, from greater than 0.0 g gallium to 15.0 ggallium per 100 g of zirconia, from greater than 0.0 g gallium to 10.0 ggallium per 100 g of zirconia, or from greater than 0.0 g gallium to 5.0g gallium per 100 g of zirconia. In some embodiments, the metal oxidecatalyst component comprises from 5.0 g gallium to 25.0 g gallium per100 g of zirconia, such as from 10.0 g gallium to 20.0 g gallium per 100g of zirconia. In some embodiments, the metal oxide catalyst componentcomprises from 0.01 g gallium per 100 g of zirconia to 5.00 g gallium to100 g zirconia, such as from 0.50 g gallium per 100 g of zirconia to5.00 g gallium to 100 g zirconia, from 1.00 g gallium per 100 g ofzirconia to 5.00 g gallium to 100 g zirconia, from 1.50 g gallium per100 g of zirconia to 5.00 g gallium to 100 g zirconia, from 2.00 ggallium per 100 g of zirconia to 5.00 g gallium to 100 g zirconia, from2.50 g gallium per 100 g of zirconia to 5.00 g gallium to 100 gzirconia, from 3.00 g gallium per 100 g of zirconia to 5.00 g gallium to100 g zirconia, from 3.50 g gallium per 100 g of zirconia to 5.00 ggallium to 100 g zirconia, from 4.00 g gallium per 100 g of zirconia to5.00 g gallium to 100 g zirconia, or from 4.50 g gallium per 100 g ofzirconia to 5.00 g gallium to 100 g zirconia.

As disclosed herein above, and without being bound to any particulartheory, it is understood that the high-surface area zirconia acts as asupport or carrier for the gallium constituent of the metal oxidecomponent, which yields a gallium and zirconia metal oxide catalystcomponent that will have selectivity for producing C₂ to C₄ olefins.Accordingly, it has been found that processes for making the gallium andzirconia metal oxide catalyst that require intimate contact of thegallium and zirconium components yield metal oxide catalyst componentsthat have improved selectivity for C₂ to C₄ olefins.

In view of the above, one method for making the gallium and zirconiummetal oxide component of the hybrid catalyst is by incipient wetnessimpregnation. In such a method, an aqueous mixture of a galliumprecursor material, which, in embodiments, may be gallium nitrate(Ga(NO₃)₃) is added to zirconia particles in a dosed amount (such asdropwise) while vigorously shaking the zirconia particles. It should beunderstood that the total amount of gallium precursor that is mixed withthe zirconia particles will be determined on the desired target amountof gallium in metal oxide catalyst component.

As discussed previously, according to some embodiments, the zirconiaparticles comprise zirconia particles having a crystalline structure. Inembodiments, the zirconia particles comprise zirconia particles having amonoclinic structure. In one or more embodiments, the zirconia particlesconsist essentially of or consist of crystalline zirconia particles, andin some embodiments, the zirconia particles consist essentially of orconsist of monoclinic zirconia particles. According to some embodiments,the zirconia particles have a BET surface area that is greater than orequal to 5 meters squared per gram (m²/g), such as greater than 10 m²/g,greater than 20 m²/g, greater than 30 m²/g, greater than 40 m²/g,greater than 50 m²/g, greater than 60 m²/g, greater than 70 m²/g,greater than 80 m²/g, greater than 90 m²/g, greater than 100 m²/g,greater than 110 m²/g, greater than 120 m²/g, greater than 130 m²/g, orgreater than 140 m²/g. According to some embodiments, the maximum BETsurface area of the zirconia particles is 150 m²/g. Accordingly, in someembodiments, the BET surface area of the zirconia particles is from 5m²/g to 150 m²/g, from 10 m²/g to 150 m²/g, from 20 m²/g to 150 m²/g,such as from 30 m²/g to 150 m²/g, from 40 m²/g to 150 m²/g, from 50 m²/gto 150 m²/g, from 60 m²/g to 150 m²/g, from 70 m²/g to 150 m²/g, from 80m²/g to 150 m²/g, from 90 m²/g to 150 m²/g, from 100 m²/g to 150 m²/g,from 110 m²/g to 150 m²/g, from 120 m²/g to 150 m²/g, from 130 m²/g to150 m²/g, or from 140 m²/g to 150 m²/g. In some embodiments, the BETsurface area of the zirconia particles is from 5 m²/g to 140 m²/g, suchas from 5 m²/g to 130 m²/g, from 5 m²/g to 120 m²/g, from 5 m²/g to 110m²/g, from 5 m²/g to 100 m²/g, from 5 m²/g to 90 m²/g, from 5 m²/g to 80m²/g, from 5 m²/g to 70 m²/g, from 5 m²/g to 60 m²/g, from 5 m²/g to 50m²/g, from 5 m²/g to 40 m²/g, from 5 m²/g to 30 m²/g, from 5 m²/g to 20m²/g, or from 5 m²/g to 10 m²/g. In some embodiments, the BET surfacearea of the zirconia particles is from 10 m²/g to 140 m²/g, from 20 m²/gto 130 m²/g, from 30 m²/g to 120 m²/g, from 40 m²/g to 110 m²/g, from 50m²/g to 100 m²/g, from 60 m²/g to 90 m²/g, or from 70 m²/g to 80 m²/g.

Once the gallium precursor and zirconia particles are adequately mixed,the metal oxide catalyst component may be dried at temperatures lessthan 200 degrees Celsius (° C.), such as less than 175° C., or less than150° C. Subsequent to the drying, the metal oxide catalyst component iscalcined at temperatures from 400° C. to 800° C., such as from 425° C.to 775° C., from 450° C. to 750° C., from 475° C. to 725° C., from 500°C. to 700° C., from 525° C. to 675° C., from 550° C. to 650° C., from575° C. to 625° C., or about 600° C. After calcining, the composition ofthe mixed metal oxide catalyst component is determined and reported as aweight of elemental gallium referenced per 100 g of phase pure zirconia(simplified to the stoichiometry of ZrO₂) as previously disclosed above.

In embodiments, the metal oxide catalyst component may be made by mixingpowders or slurries of a gallium precursor (such as gallium nitrate orgallium oxide) and zirconia. According to some embodiments, the zirconiaparticles comprise zirconia particles having a crystalline structure. Inembodiments, the zirconia particles comprise zirconia particles having amonoclinic structure. In one or more embodiments, the zirconia particlesconsist essentially of or consist of crystalline zirconia particles, andin some embodiments, the zirconia particles consist essentially of orconsist of monoclinic zirconia particles. The zirconia particles may, inembodiments, have the BET surface areas disclosed above. The powders orslurries may be vigorously mixed at high temperatures such from roomtemperature (approximately 23° C.) to 100° C. After the powders orslurries have been adequately mixed, the metal oxide catalyst componentmay be dried and calcined at temperatures from 400° C. to 800° C., suchas from 425° C. to 775° C., from 450° C. to 750° C., from 475° C. to725° C., from 500° C. to 700° C., from 525° C. to 675° C., from 550° C.to 650° C., from 575° C. to 625° C., or about 600° C. After calcining,the composition of the mixed metal oxide catalyst component isdetermined and reported as a weight of elemental gallium in reference to100 g of phase pure zirconia (simplified to the stoichiometry of ZrO₂)as disclosed above.

It should be understood that according to embodiments, the metal oxidecatalyst component may be made by other methods that eventually lead tointimate contact between the gallium and zirconia. Some non-limitinginstances include vapor phase deposition of Ga-containing precursors(either organic or inorganic in nature), followed by their controlleddecomposition. Similarly, processes for dispersing liquid gallium metalcan be amended by those skilled in the art to develop Ga—ZrO₂.

Elements other than zirconia and gallium may, in some embodiments, bepresent in the metal oxide catalyst component containing phase purezirconia and gallium. Such elements may be introduced to the phase purezirconia before, during or after introducing gallium to the composition.Sometimes such elements are added to direct and stabilize thecrystallization of zirconia phase (e.g., Y-stabilized tetragonal ZrO₂).In other instances, additional elements from the group of rare earth,alkaline, and/or transition metals are co-deposited with galliumprecursor or introduced only when Ga—ZrO₂ mixed composition has beenprepared in the first place. Similarly, the metal oxide catalystcomponent may also contain residual or be purposefully modified withnon-metal dopants like, for example, sulfur (present as, for example,oxoanion SO₄), chlorine (Cl), phosphorus (P), or mixtures thereof may bepresent in the zirconia support or remain after using as an element ofthe precursor intended to introduce gallium or other metals into thephase-pure zirconia.

In one or more embodiments, after the metal oxide catalyst component hasbeen formed—such as, for example, by the methods disclosed above—themetal oxide catalyst component is physically mixed with a microporouscatalyst component. The microporous catalyst component is, inembodiments, selected from molecular sieves having 8-MR pore openingsand having a framework type selected from the group consisting of thefollowing framework types CHA, AEI, AFX, ERI, LTA, UFI, RTH, EDI, GIS,MER, RHO, and combinations thereof, the framework types corresponding tothe naming convention of the International Zeolite Association. Itshould be understood that in embodiments, both aluminosilicate andsilicoaluminophosphate frameworks may be used. Some embodiments mayinclude tetrahedral aluminosilicates, ALPOs (such as, for example,tetrahedral aluminophosphates), SAPOs (such as, for example, tetrahedralsilicoaluminophosphates), and silica-only based tectosilicates. Incertain embodiments, the microporous catalyst component may besilicoaluminophosphate having a Chabazite (CHA) framework type. Examplesof these may include, but are not necessarily limited to: CHAembodiments selected from SAPO-34 and SSZ-13; and AEI embodiments suchas SAPO-18. Combinations of microporous catalyst components having anyof the above framework types may also be employed. It should beunderstood that the microporous catalyst component may have differentmembered ring pore opening depending on the desired product. Forinstance, microporous catalyst component having 8-MR to 12-MR poreopenings could be used depending on the desired product. However, toproduce C₂ to C₄ olefins, a microporous catalyst component having 8-MRpore openings is used in embodiments.

The metal oxide catalyst component and the microporous catalystcomponent of the hybrid catalyst may be mixed together by any suitablemeans, such as, for example, by physical mixing—such as shaking,stirring, or other agitation. The metal oxide catalyst component may, inembodiments, comprise from 1.0 wt % to 99.0 wt % of the hybrid catalyst,such as from 5.0 wt % to 99.0 wt %, from 10.0 wt % to 99.0 wt %, from15.0 wt % to 99.0 wt %, from 20.0 wt % to 99.0 wt %, from 25.0 wt % to99.0 wt %, from 30.0 wt % to 99.0 wt %, from 35.0 wt % to 99.0 wt %,from 40.0 wt % to 99.0 wt %, from 45.0 wt % to 99.0 wt %, from 50.0 wt %to 99.0 wt %, from 55.0 wt % to 99.0 wt %, from 60.0 wt % to 99.0 wt %,from 65.0 wt % to 99.0 wt %, from 70.0 wt % to 99.0 wt %, from 75.0 wt %to 99.0 wt %, from 80.0 wt % to 99.0 wt %, from 85.0 wt % to 99.0 wt %,from 90.0 wt % to 99.0 wt %, or from 95.0 wt % to 99.0 wt %. In someembodiments, the metal oxide catalyst component comprises from 1.0 wt %to 95.0 wt % of the hybrid catalyst, such as from 1.0 wt % to 90.0 wt %,from 1.0 wt % to 85.0 wt %, from 1.0 wt % to 80.0 wt %, from 1.0 wt % to75.0 wt %, from 1.0 wt % to 70.0 wt %, from 1.0 wt % to 65.0 wt %, from1.0 wt % to 60.0 wt %, from 1.0 wt % to 55.0 wt %, from 1.0 wt % to 50.0wt %, from 1.0 wt % to 45.0 wt %, from 1.0 wt % to 40.0 wt %, from 1.0wt % to 35.0 wt %, from 1.0 wt % to 30.0 wt %, from 1.0 wt % to 25.0 wt%, from 1.0 wt % to 20.0 wt %, from 1.0 wt % to 15.0 wt %, from 1.0 wt %to 10.0 wt %, or from 1.0 wt % to 5.0 wt %. In some embodiments, themetal oxide catalyst component comprises from 5.0 wt % to 95.0 wt % ofthe hybrid catalyst, such as from 10.0 wt % to 90.0 wt %, from 15.0 wt %to 85.0 wt %, from 20.0 wt % to 80.0 wt %, from 25.0 wt % to 75.0 wt %,from 30.0 wt % to 70.0 wt %, from 35.0 wt % to 65.0 wt %, from 40.0 wt %to 60.0 wt %, or from 45.0 wt % to 55.0 wt %.

After the metal oxide catalyst component has been formed and combinedwith a microporous catalyst component to form a hybrid catalyst, thehybrid catalyst may be used in methods for converting carbon in acarbon-containing feed stream to C₂ to C₄ olefins. Such processes willbe described in more detail below.

According to embodiments, a feed stream is fed into a reaction zone, thefeed stream comprising hydrogen (H₂) gas and a carbon-containing gasselected from carbon monoxide (CO), carbon dioxide (CO2), andcombinations thereof. In some embodiments, the H₂ gas is present in thefeed stream in an amount of from 10 volume percent (vol %) to 90 vol %,based on combined volumes of the H₂ gas and the gas selected from CO,CO₂, and combinations thereof. The feed stream is contacted with ahybrid catalyst as disclosed and described herein in the reaction zone.The hybrid catalyst comprises a metal oxide catalyst componentcomprising gallium oxide and zirconia; and a microporous catalystcomponent.

It should be understood that the activity of the hybrid catalyst will behigher for feed streams containing CO as the carbon-containing gas, andthat the activity of the hybrid catalyst decreases as a larger portionof the carbon-containing gas in the feed stream is CO₂. However, that isnot to say that the hybrid catalyst disclosed and described hereincannot be used in methods where the feed stream comprises CO₂ as all, ora large portion, of the carbon-containing gas.

The feed stream is contacted with the hybrid catalyst in the reactionzone under reaction conditions sufficient to form a product streamcomprising C₂ to C₄ olefins. The reaction conditions comprise atemperature within the reaction zone ranging, according to one or moreembodiments, from 300° C. to 500° C., such as from 300° C. to 475° C.,from 300° C. to 450° C., from 300° C. to 425° C., from 300° C. to 400°C., from 300° C. to 375° C., from 300° C. to 350° C., or from 300° C. to325° C. In other embodiments, the temperature within the reaction zoneis from 325° C. to 500° C., from 350° C. to 500° C., from 375° C. to500° C., from 400° C. to 500° C., from 425° C. to 500° C., from 450° C.to 500° C., or from 475° C. to 500° C. In yet other embodiments, thetemperature within the reaction zone is from 300° C. to 500° C., such asfrom 325° C. to 475° C., from 350° C. to 450° C., or from 360° C. to440° C.

The reaction conditions also, in embodiments, include a pressure insidethe reaction zone of at least 1 bar (100 kilopascals (kPa), such as atleast 5 bar (500 kPa), at least 10 bar (1,000 kPa), at least 15 bar(1,500 kPa), at least 20 bar (2,000 kPa), at least 25 bar (2,500 kPa),at least 30 bar (3,000 kPa), at least 35 bar (3,500 kPa), at least 40bar (4,000 kPa), at least 45 bar (4,500 kPa), at least 50 bar (5,000kPa), at least 55 bar (5,500 kPa), at least 60 bar (6,000 kPa), at least65 bar (6,500 kPa), at least 70 bar (7,000 kPa), at least 75 bar (7,500kPa), at least 80 bar (8,000 kPa), at least 85 bar (8,500 kPa), at least90 bar (9,000 kPa), at least 95 bar (9,500 kPa), or at least 100 bar(10,000 kPa). In other embodiments, the reaction conditions include apressure inside the reaction zone is from 5 bar (500 kPa) to 100 bar(10,000 kPa), such as from 10 bar (1,000 kPa) to 95 bar (9,500 kPa),from 15 bar (1,500 kPa) to 90 bar (9,000 kPa), from 20 bar (2,000 kPa)to 85 bar (8,500 kPa), from 25 bar (2,500 kPa) to 80 bar (8,000 kPa),from 30 bar (3,000 kPa) to 75 bar (7,500 kPa), from 35 bar (3,500 kPa)to 70 bar (7,000 kPa), from 40 bar (4,000 kPa) to 65 bar (6,500 kPa),from 45 bar (4,500 kPa) to 60 bar (6,000 kPa), or from 50 bar (5,000kPa) to 55 bar (5,500 kPa). In some embodiments, the pressure inside thereaction zone is from 20 bar (2,000 kPa) to 60 bar (6,000 kPa).

According to embodiments, the gas hour space velocity (GHSV) within thereaction zone is from 1,200 per hour (/h) to 12,000/h, such as from1,500/h to 10,000/h, from 2,000/h to 9,500/h, from 2,500/h to 9,000/h,from 3,000/h to 8,500/h, from 3,500/h to 8,000/h, from 4,000/h to7,500/h, from 4,500/h to 7,000/h, from 5,000/h to 6,500/h, or from5,500/h to 6,000/h. In some embodiments the GHSV within the reactionzone is from 1,800/h to 3,600/h, such as from 2,000/h to 3,600/h, from2,200/h to 3,600/h, from 2,400/h to 3,600/h, from 2,600/h to 3,600/h,from 2,800/h to 3,600/h, from 3,000/h to 3,600/h, from 3,200/h to3,600/h, or from 3,400/h to 3,600/h. In some embodiments, the GHSVwithin the reaction zone is from 1,800/h to 3,400/h, such as from1,800/h to 3,200/h, from 1,800/h to 3,000/h, from 1,800/h to 2,800/h,from 1,800/h to 2,600/h, from 1,800/h to 2,400/h, from 1,800/h to2,200/h, or from 1,800/h to 2,000/h. In some embodiments, the GHSVwithin the reaction is from 2,000/h to 3,400/h, such as from 2,200/h to3,200/h, from 2,400/h to 3,000/h, or from 2,600/h to 2,800/h.

By using hybrid catalysts disclosed and described herein along with theprocess conditions disclosed and described herein, improved C₂ to C₄olefin yields and carbon conversion may be achieved. For example, inembodiments where hydrogen to carbon monoxide Hz/CO ratios range from 2to 5, such as greater than 2.2 and less than 3.8, or greater than 2.8and less than 3.4, where temperatures range from 360° C. to 460° C.,such as from 380° C. to 440° C., or from 400° C. to 420° C., andpressure ranges from 5 to 100 bars, such as from 20 to 80 bars, or from30 to 60 bars. Using such conditions, the C₂ to C₄ olefin yield isgreater than or equal to 4.0 mol %, such as greater than or equal to 5.0mol %, greater than or equal to 7.0 mol %, greater than or equal to 10.0mol %, greater than or equal to 12.0 mol %, greater than or equal to15.0 mol %, greater than or equal to 17.0 mol %, greater than or equalto 20.0 mol %, greater than or equal to 22.0 mol %, greater than orequal to 25.0 mol %, greater than or equal to 27.0 mol %, greater thanor equal to 30.0 mol %, greater than or equal to 32.0 mol %, or greaterthan or equal to 35.0 mol %. In some embodiments, the maximum C₂ to C₄olefin yield is 50.0 mol %. Thus, in some embodiments, the C₂ to C₄olefin yield is from greater than or equal to 4.0 mol % to 50.0 mol %,such as from 5.0 mol % to 50.0 mol %, from 7.0 mol % to 50.0 mol %, from10.0 mol % to 50.0 mol %, from 12.0 mol % to 50.0 mol %, from 15.0 mol %to 50.0 mol %, from 17.0 mol % to 50.0 mol %, from 20.0 mol % to 50.0mol %, from 22.0 mol % to 50.0 mol %, from 25.0 mol % to 50.0 mol %,from 27.0 mol % to 50.0 mol %, from 30.0 mol % to 50.0 mol %, from 32.0mol % to 50.0 mol %, from 35.0 mol % to 50.0 mol %, from 37.0 mol % to50.0 mol %, from 40.0 mol % to 50.0 mol %, from 42.0 mol % to 50.0 mol%, from 45.0 mol % to 50.0 mol %, or from 47.0 mol % to 50.0 mol %.

In embodiments, using hybrid catalysts disclosed and described hereinalong with the process conditions disclosed and described herein, thecarbon conversion may be improved. Within the process ranges disclosed,the conversion of the feed containing carbon oxides and hydrogen can becarried out in a series of rectors with an intermediate knock-out ofwater by-product by the means of e.g., phase separation, membraneseparation, or some type of water-selective absorptive process. Furtherdirecting the partially converted and water-free effluent to thesubsequent reactor in series and repeating this manner of technologicaloperations will have an overall effect of enhancing the olefin yield.For example, in embodiments where two to four such operations arecarried out the overall olefin yield may be greater than or equal to50.0 mol %, such as greater than or equal to 52.0 mol %, greater than orequal to 55.0 mol %, greater than or equal to 57.0 mol %, greater thanor equal to 60.0 mol %, greater than or equal to 62.0 mol %, greaterthan or equal to 65.0 mol %, greater than or equal to 67.0 mol %,greater than or equal to 70.0 mol %, greater than or equal to 72.0 mol%, greater than or equal to 75.0 mol %, greater than or equal to 77.0mol %, greater than or equal to 80.0 mol %, or greater than or equal to85.0 mol %. In some embodiments, the maximum carbon conversion is 95.0mol %. Accordingly, in embodiments, the carbon conversion may be fromgreater than or equal to 50.0 mol % to 95.0 mol %, such as from 52.0 mol% to 95.0 mol %, from 55.0 mol % to 95.0 mol %, from 57.0 mol % to 95.0mol %, from 60.0 mol % to 95.0 mol %, from 62.0 mol % to 95.0 mol %,from 65.0 mol % to 95.0 mol %, from 67.0 mol % to 95.0 mol %, from 60.0mol % to 95.0 mol %, from 72.0 mol % to 95.0 mol %, from 75.0 mol % to95.0 mol %, from 77.0 mol % to 95.0 mol %, from 80.0 mol % to 95.0 mol%, from 82.0 mol % to 95.0 mol %, from 85.0 mol % to 95.0 mol %, from87.0 mol % to 95.0 mol %, from 90.0 mol % to 95.0 mol %, or from 92.0mol % to 95.0 mol %.

EXAMPLES

Embodiments will be further clarified by the following examples andcomparative examples. In all examples and comparative examples hybridcatalysts were prepared by mixing the given amount of mixed oxidecatalyst component (60-80 mesh) with microporous catalyst componentSAPO-34 (60-80 mesh). The amounts can be found in the tables below.However, it should be understood that in some comparative examples,SAPO-34 is not included. This is indicated by a value of zero (“0”) inthe tables below.

Comparative Example 1

Composite catalysts with SAPO-34 microporous catalyst components andeither bulk In₂O₃, bulk Ga₂O₃, or bulk ZrO₂; physical mixture of bulkGa₂O₃ and ZrO₂ without microporous catalyst component.

Table 1a shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO of approximately 2.0;pressure of 20 bar (2,000 kPa); temperature of 390° C., and GHSV equals1200/h. The metal oxide catalyst used in the comparative example is abulk metal oxide as shown in Table 1a. The indium oxide used in thiscomparative example was commercially available from Aldrich, product no.63 2317, and the gallium oxide used was commercially available fromAldrich, product no. 20,333-5. Prior to this test each of the startingcomponents were compacted, crushed and sized to provide 60-80 meshfractions for the preparation of physical mixtures. Next, by combining150 μL of SAPO-34 (approximately, sized particles) and adding 150 μL ofeither indium oxide or gallium oxide (each measured approximately, sizedparticles) hybrid catalysts were prepared upon gentle shaking ofparticles together in a vial. The table below references the catalyticperformance of the dual-particle bed of SAPO-34 admixed with either ofthe neat oxides including each component weight.

TABLE 1a Oxide component Olefin present in SAPO-34 Oxide YieldSelectivity Selectivity Fraction in admixture weight weight C₂-C₃Olefins CO Conv. C₂-C₃ Olefin C₂-C₃ Paraffin [C₂-C₃ with SAPO-34 (mg)(mg) [C mol %] [C mol. %] [C mol %] [C mol %] Product] ToS = 12-24 hrsIn₂O₃ 87 201 9.8 27.3 37.2 9.3 0.80 Ga₂O₃ 79 109 0.8 19.4 4.1 34.2 0.11ToS = 48-72 hrs In₂O₃ 87 201 0.2 1.2 16.1 8.5 0.65 Ga₂O₃ 79 109 0.8 18.94.2 34.1 0.11 Oxide component present in Selectivity SelectivitySelectivity Selectivity admixture CH₄ C₄ Olefins C₄-C₅ Paraffins CO₂with SAPO-34 [C mol %] [C mol %] [C mol %] [C mol %] ToS = 12-24 hrsIn₂O₃ 2.9 1.1 0.8 51.1 Ga₂O₃ 2.6 0.0 9.2 49.6 ToS = 48-72 hrs In₂O₃ 34.90.0 0.0 43.6 Ga₂O₃ 3.1 0.0 9.4 48.7

Table 1b shows results for a process for converting syngas into olefins,at the following process conditions: H₂/CO of approximately 3.0;pressure of 40 bar (4,000 kPa); temperature of 420° C.; and GHSV equals2400/h and compares intrinsic performance of either zirconia or galliaadmixed with SAPO-34. The zirconium oxide used in this comparativeexample was commercially available monoclinic ZrO₂, (vendor NORPRO,product code SZ39114) and contains some Hf impurity (approximately 2.45wt %). Before being used, the zirconium oxide was dispersed in water,dried, and calcined at 550° C. The gallium oxide used in thiscomparative example was commercially available gallium oxide (availableas AlfaAesar, product no. 10508). Before being used, the gallium oxideis dispersed in water, dried, and calcined at 550° C. Prior to this testboth oxides and the sieve were compacted, crushed and sieved to provide60-80 mesh fractions of the starting components. Next, by measuringvolumetrically approximately 200 μL of SAPO-34 (sized particles) andadding either 200 μL of zirconium oxide (sized particles) or 200 μL ofgallium oxide (sized particles) hybrid catalysts were prepared upongentle shaking. The table below references the catalytic performance ofthe dual-particle bed of SAPO-34 admixed with either of the neat oxides.

TABLE 1b Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ZrO₂ 104 252 9.2 23.7 38.8 13.7 Ga₂O₃ 100 179 3.940.6 9.5 39.3 ToS = 72-96 hrs ZrO₂ 104 252 10.0 26.1 38.3 14.7 Ga₂O₃ 100179 3.4 38.0 8.8 39.5 Oxide component Olefin present in Fraction inSelectivity Selectivity Selectivity Selectivity admixture [C₂-C₃ CH₄ C₄Olefins C₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [Cmol %] [C mol %] ToS = 24-48 hrs ZrO₂ 0.7 1.4 4.1 1.0 40.9 Ga₂O₃ 0.2 2.54.4 6.2 38.1 ToS = 72-96 hrs ZrO₂ 0.7 1.5 4.1 1.0 40.4 Ga₂O₃ 0.2 3.0 3.76.8 38.3Table 1c shows results for a process for converting syngas into at thefollowing process conditions: H₂/CO of approximately 3.0; pressure of 40bar (4,000 kPa); temperature of 420° C.; and GHSV equals 2400/h. Toprepare a dual-particle catalyst bed Zirconium oxide (20 mg) and galliumoxide (80 mg) were physically mixed together to form a mixture ofparticles (100 mg). To prepare this combination the ZrO₂ and Ga₂O₃materials referenced in the example 1b, were used. To furtherdifferentiate this combination, the catalyst bed did not contain anySAPO-34 component.

TABLE 1c Oxide SAPO-34 Oxide Yield Selectivity Selectivity componentsWeight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ Olefin C₂-C₃ Paraffin present(mg) (mg) [C mol %] [C mol. %] [C mol %] [C mol %] ToS = 24-48 hrs ~18.4g Ga/100 g 0.0 100.0 0.6 7.4 8.5 7.5 ZrO₂ ToS = 72-96 hrs ~18.4 g Ga/100g 0.0 100.0 0.6 7.4 7.7 6.7 ZrO₂ Olefin Oxide Fraction in SelectivitySelectivity Selectivity Selectivity components [C₂-C₃ CH₄ C₄ OlefinsC₄-C₅ Paraffins CO₂ present Product] [C mol %] [C mol %] [C mol %] [Cmol %] ToS = 24-48 hrs ~18.4 g Ga/100 g 0.53 4.3 2.5 2.2 39.2 ZrO₂ ToS =72-96 hrs ~18.4 g Ga/100 g 0.53 4.2 2.6 3.6 38.5 ZrOi

Comparative Example 1a demonstrates intrinsic properties of neat bulkoxides of elements from Group 13 of the periodic table of elements uponformulation of dual-particle bed with SAPO-34. Comparative example 1bbenchmarks intrinsic properties of neat zirconia against neat gallia incombination with SAPO-34 in dual-particle bed application. Thiscomparative example show that different neat oxides in combination withSAPO-34 results in very different catalytic behavior in the conversionof syngas to hydrocarbons. Notably, (1) neat In₂O₃ has a some initialhigh activity and selectivity towards olefins, but short life processtime and the hybrid system deactivated rather quickly; (2) neatmonoclinic ZrO₂ showed a high selectivity towards olefins and long lifeon stream but poor activity; (3) neat Ga₂O₃ showed moderate activity andvery poor selectivity towards olefins and high selectivity to paraffinsand at the same time could convert syngas over long process times thanindium oxide. Furthermore, the comparative example 1c shows that aphysical mixture of gallium and zirconium oxides without microporouscatalyst component (SAPO-34) has also poor activity and low selectivitytowards olefins.

Comparative Example 2

Table 2a shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO of approximately 2;temperature of 390° C.; pressure of 20 bar (2,000 kPa); and GHSV equals1200/h. The hybrid catalysts were prepared from the sized (60-80 mesh)particles of SAPO-34 (150 μL volumetric measure of sized particles orapproximately 75 mg each time) and sized particles of various mixedmetal oxide catalysts. The mixed oxides were featuring gallium andlacking zirconium. The oxides were prepared by incipient wetnessimpregnation of aqueous solutions of gallium nitrate precursor ontooxide of either silicon, titanium, or niobium followed by drying andcalcination (500 dig). The amounts of the sized 60-80 mesh mixed oxideparticles used to prepare hybrid catalyst beds with SAPO-34 wereapproximately 150 μL volumetric measure each time. Because of variedapparent densities of different carrier oxides, the weight of the oxidesalso varied. Hybrid catalysts were prepared upon gentle shaking of sizedparticles together in a vial.

TABLE 2a Oxide composition SAPO-34 Oxide Yield Selectivity Selectivityin admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ Olefin C₂-C₃Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [C mol %]ToS = 24-48 hrs ~3.8 g Ga/100 g 70 49.7 0.3 2.6 12.0 16.5 SiO₂ ~8.1 gGa/100 g 72 53.0 0.2 1.7 14.6 14.1 SiO₂ ~11.6 g Ga/100 g  70 54.0 0.33.5 10.0 16.6 SiO₂ ~9.7 g Ga/100 g 82 101.7 0.5 29.0 1.8 36.0 TiO₂ ~3.5g Ga/100 g 81 103.1 1.0 26.8 3.9 31.5 TiO₂ ~3.8 g Ga/100 g 88 144.1 0.13.9 2.3 14.4 Nb₂O₅ ToS = 72-96 hrs ~3.8 g Ga/100 g 70 49.7 0.3 2.7 10.516.5 SiO₂ ~8.1 g Ga/100 g 72 53.0 0.2 1.8 12.5 12.0 SiO₂ ~11.6 g Ga/100g  70 54.0 0.3 3.3 8.7 16.4 SiO₂ ~9.7 g Ga/100 g 82 101.7 0.5 27.2 1.935.6 TiO₂ ~3.5 g Ga/100 g 81 103.0 1.0 25.5 4.1 31.3 TiO₂ ~3.8 g Ga/100g 88 144.1 0.1 3.9 2.3 13.8 Nb₂O₅                ToS = 100-120 hrs,H₂/CO ratio changed to 3, Pressure changed to 30 bar ~9.7 g Ga/100 g 82101.7 0.5 33.2 1.5 37.3 TiO₂ ~3.5 g Ga/100 g 81 103.1 0.9 36.9 2.5 35.3TiO₂ Oxide Olefin composition Fraction in Selectivity SelectivitySelectivity Selectivity in admixture [C₂-C₃ CH₄ C₄ Olefins C₄-C₅Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %] [C mol%] ToS = 24-48 hrs ~3.8 g Ga/100 g 0.42 31.6 0.0 3.1 33.6 SiO₂ ~8.1 gGa/100 g 0.51 21.2 0.0 0.0 45.2 SiO₂ ~11.6 g Ga/100 g  0.38 34.1 0.0 2.634.8 SiO₂ ~9.7 g Ga/100 g 0.05 7.4 0.3 7.3 47.2 TiO₂ ~3.5 g Ga/100 g0.11 9.3 0.3 7.0 47.6 TiO₂ ~3.8 g Ga/100 g 0.14 34.4 0.0 0.0 48.4 Nb₂O₅ToS = 72-96 hrs ~3.8 g Ga/100 g 0.39 32.6 0.0 2.9 32.0 SiO₂ ~8.1 gGa/100 g 0.51 18.8 0.0 0.0 50.3 SiO₂ ~ 11.6 g Ga/100 g  0.35 34.8 0.02.7 33.7 SiO₂ ~9.7 g Ga/100 g 0.05 8.3 0.3 6.9 47.0 TiO₂ ~3.5 g Ga/100 g0.12 9.9 0.4 6.7 47.0 TiO₂ ~3.8 g Ga/100 g 0.14 33.8 0.0 0.0 49.3 Nb₂O₅               ToS = 100-120 hrs, H₂/CO ratio changed to 3, Pressurechanged to 30 bar ~9.7 g Ga/100 g 0.04 9.3 0.4 7.2 44.2 TiO₂ ~3.5 gGa/100 g 0.07 8.4 0.1 6.9 45.7 TiO₂

Table 2b shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO of approximately 3;temperature of 420° C.; pressure of 40 bar (4,000 kPa); and GHSV equals2400/h. The amounts of the sized 60-80 mesh mixed oxide particles usedto prepare hybrid catalyst beds with SAPO-34 were approximately 200 μLvolumetric measure each time. Hybrid catalysts were prepared upon gentleshaking of sized particles together in a vial.

TABLE 2b Oxide component Olefin present in SAPO-34 Oxide YieldSelectivity Selectivity Fraction in admixture Weight Weight C₂-C₃Olefins CO Conv. C₂-C₃ Olefin C₂-C₃ Paraffin [C₂-C₃ with SAPO-34 (mg)(mg) [C mol %] [C mol. %] [C mol %] [C mol %] Product] ToS = 24-48 hrs~5.2 g Ga and 126 150 3.5 58.9 5.9 42.4 0.12 ~5.7 g Zn/100 g TiO₂  9.4 gGa/100 g 127 146 1.4 46.8 3.1 29.4 0.10 TiO₂ ToS = 72-86 hrs ~5.2 g Gaand 126 150 3.0 58.1 5.2 41.2 0.11 ~5.7 g Zn/100 g TiO₂  9.4 g Ga/100 g127 146 1.4 43.8 3.1 27.5 0.10 TiO₂ Oxide component present inSelectivity Selectivity Selectivity Selectivity admixture CH₄ C₄ OlefinsC₄-C₅ Paraffins CO₂ with SAPO-34 [C mol %] [C mol %] [C mol %] [C mol %]ToS = 24-48 hrs ~5.2 g Ga and 6.0 1.6 8.3 35.8 ~5.7 g Zn/100 g TiO₂  9.4g Ga/100 g 18.9 1.0 5.9 41.7 TiO₂ ToS = 72-96 hrs ~5.2 g Ga and 7.5 1.49.1 35.6 ~5.7 g Zn/100 g TiO₂ ~9.4 g Ga/100 g 21.2 0.9 5.5 41.8 TiO₂

For composite catalysts with SAPO-34 as the microporous catalystcomponent and a Ga-MOx metal oxide catalyst component. Each of theGa-MOx metal oxide catalyst components was prepared by processingcrystalline powders of either Y₂O₃, La₂O₃, CeO₂, Cr₂O₃, MgAl₂O₄, or MgOand Ga₂O₃ in slurring fine particles in deionized water, drying, andcalcining at 550° C.

Table 2c shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 3;temperature of 420° C.; pressure of 40 bar (4,000 kPa); and GHSV equals2400/h. The amounts of the sized 60-80 mesh mixed oxide particles usedto prepare hybrid catalyst beds with SAPO-34 were approximately 200 μLvolumetric measure each time. Hybrid catalysts were prepared upon gentleshaking of sized particles together in a vial.

TABLE 2c Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~12.9 wt % Ga, 101 147 1.3 19.4 6.5 40.3 ~62.3 wt% Y,  balance - oxygen ~15.4 wt % Ga, 116 190 0.9 16.7 5.3 38.8 ~66.5 wt% La,  balance - oxygen ~13.0 wt % Ga, 111 211 3.0 26.0 11.6 37.5 ~66.1wt % Ce, balance - oxygen ~11.4 wt % Ga, 99 152 1.8 17.8 10.1 43.9 ~57.4wt % Cr,  balance - oxygen ~10.6 wt % Ga, 98 183 0.8 5.8 13.1 24.7 ~31.3wt % Al,   ~15.7 wt % Mg, balance - oxygen ~17.6 wt % Ga, 95 218 0.9 9.39.5 31.9  ~45.2 wt % Mg, balance - oxygen ToS = 72-96 hrs ~12.9 wt % Ga,101 147 1.1 19.1 6.0 38.1 ~62.3 wt % Y,  balance - oxygen ~15.4 wt % Ga,116 190 0.9 16.3 5.7 36.2 ~66.5 wt % La,  balance - oxygen ~13.0 wt %Ga, 111 211 2.4 24.8 9.7 39.1 ~66.1 wt % Ce, balance - oxygen ~11.4 wt %Ga, 99 152 1.4 16.8 8.6 44.9 ~57.4 wt % Cr,  balance - oxygen ~10.6 wt %Ga, 98 183 0.8 5.9 12.8 21.3 ~31.3 wt % Al,   ~15.7 wt % Mg, balance -oxygen ~17.6 wt % Ga, 95 218 0.9 8.6 10.4 28.2  ~45.2 wt % Mg, balance -oxygen Oxide component Olefin present in Fraction in SelectivitySelectivity Selectivity Selectivity admixture [C₂-C₃ CH₄ C₄ OlefinsC₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %][C mol %] ToS = 24-48 hrs ~12.9 wt % Ga, 0.14 4.5 2.6 6.8 39.4 ~62.3 wt% Y, balance - oxygen ~15.4 wt % Ga, 0.12 5.3 1.0 9.1 40.4 ~66.5 wt %La, balance - oxygen ~13.0 wt % Ga, 0.24 3.4 4.9 4.0 38.6 ~66.1 wt % Ce,balance - oxygen ~11.4 wt % Ga, 0.19 2.4 4.0 5.2 34.4 ~57.4 wt % Cr,balance - oxygen ~10.6 wt % Ga, 0.35 15.1 0.0 6.7 40.5 ~31.3 wt % Al,~15.7 wt % Mg, balance - oxygen ~17.6 wt % Ga, 0.23 9.0 1.8 8.8 39.0~45.2 wt % Mg, balance - oxygen Oxide component Olefin present inFraction in Selectivity Selectivity Selectivity Selectivity admixture[C₂-C₃ CH₄ C₄ Olefins C₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol%] [C mol %] [C mol %] [C mol %] ToS = 72-96 hrs ~12.9 wt % Ga, 0.14 5.81.9 8.2 40.0 ~62.3 wt % Y, balance - oxygen ~15.4 wt % Ga, 0.14 7.1 0.810.1 40.2 ~66.5 wt % La, balance - oxygen ~13.0 wt % Ga, 0.20 4.2 3.84.8 38.5 ~66.1 wt % Ce, balance - oxygen ~11.4 wt % Ga, 0.16 3.0 3.1 6.234.2 ~57.4 wt % Cr, balance - oxygen ~10.6 wt % Ga, 0.38 20.1 0.0 5.939.8 ~31.3 wt % Al, ~15.7 wt % Mg, balance - oxygen ~17.6 wt % Ga, 0.2712.6 1.4 9.1 38.3 ~45.2 wt % Mg, balance - oxygen

Example 1

This example shows the effects of hybrid catalysts formed from anSAPO-34 microporous catalyst component, and a metal oxide catalystcomponent comprising ZrO₂-supported gallium catalysts (monoclinic-ZrO₂,BET surface area of approximately 50 m²/g). The amounts of the sized60-80 mesh mixed oxide particles used to prepare hybrid catalyst bedsare reported in the Table 3a and 3b. Hybrid catalysts were prepared upongentle shaking of particles together in a vial.

Table 3a shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 2;temperature of 390° C.; pressure of 20 bar (2,000 kPa); and GHSV equals1200/h.

TABLE 3a Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~9.3 g Ga/100 g 80 170 15.5 39.8 38.8 9.3 ZrO₂~3.3 g Ga/100 g 80 159 14.3 36.4 39.2 9.0 ZrO₂ ToS = 72-96 hrs ~9.3 gGa/100 g 80 170 14.9 38.5 38.6 9.0 ZrO₂ ~3.3 g Ga/100 g 80 159 13.4 34.439.1 8.6 ZrO₂ Oxide component Olefin present in Fraction in SelectivitySelectivity Selectivity Selectivity admixture [C₂-C₃ CH₄ C₄ OlefinsC₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %][C mol %] ToS = 24-48 hrs ~9.3 g Ga/100 g 0.81 3.7 1.7 1.0 48.0 ZrO₂~3.3 g Ga/100 g 0.81 2.3 1.8 0.9 48.8 ZrO₂ ToS = 72-96 hrs ~9.3 g Ga/100g 0.81 4.0 1.7 0.8 48.4 ZrO₂ ~3.3 g Ga/100 g 0.82 2.5 1.9 0.8 49.0 ZrO₂

Table 3b shows the results a process for converting syngas into olefinswith the following process conditions: syngas process H₂/COapproximately 3; temperature of 420° C.; pressure of 40 bar; and GHSVequals 2400/h.

TABLE 3b Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~9.3 g Ga/100 g 130 234 14.9 72.5 20.5 33.9 ZrO₂~1.7 g Ga and 125 225 13.6 78.7 17.3 36.7 ~1.9 g Zn/100 g ZrO₂  3.3 gGa/100 g 127 220 19.3 74.7 25.8 29.1 ZrO₂ ToS = 72-96 hrs  ~9.3g Ga/100g 130 234 14.7 71.7 20.5 33.7 ZrO₂ ~1.7 g Ga and 125 225 9.8 78.0 12.540.9 ~1.9 g Zn/100 g ZrO₂  3.3 g Ga/100 g 127 220 18.8 74.5 25.2 29.8ZrO₂ Oxide component Olefin present in Fraction in SelectivitySelectivity Selectivity Selectivity admixture [C₂-C₃ CH₄ C₄ OlefinsC₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %][C mol %] ToS = 24-48 hrs ~9.3 g Ga/100 g 0.38 1.4 5.4 3.2 35.6 ZrO₂~1.7 g Ga and 0.32 2.4 4.9 4.0 34.6 ~1.9 g Zn/100 g ZrO₂  3.3 g Ga/100 g0.47 1.4 5.7 2.6 35.3 ZrO₂ ToS = 72-96 hrs ~9.3 g Ga/100 g 0.38 1.6 5.33.3 35.6 ZrO₂ ~1.7 g Ga and 0.23 3.0 4.1 5.0 34.5 ~1.9 g Zn/100 g ZrO₂ 3.3 g Ga/100 g 0.46 1.6 5.7 2.8 35.0 ZrO₂

Example 1 demonstrates that Ga—ZrO₂ microporous prepared in variousloadings deposited on monoclinic zirconia and tested with SAPO-34 as themicroporous catalyst component under varied conditions of feeds (H₂/COapproximately 2 or approximately 3) and process (temperature andpressure). This example shows the effectiveness of lower loadings of Gaas well as the effectiveness of a zirconia support in the metal oxidecatalyst component.

Example 2

This example included catalysts with SAPO-34 as the microporous catalystcomponent and featuring ZrO₂-supported gallium as the metal oxidecatalyst component (monoclinic-ZrO₂, BET surface area approximately 100m²/g) using an impregnation approach. The amounts of the sized 60-80mesh mixed oxide particles used to prepare hybrid catalyst beds arereported in the Table 4a and 4b. Hybrid catalysts were prepared upongentle shaking of particles together in a vial.

Table 4a shows the results a process for converting syngas into olefinswith the following process conditions H₂/CO approximately 2; temperatureof 390° C.; pressure of 20 bar (2,000 kPa); and GHSV equals 1200/h.

TABLE 4a Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~0.3 g Ga/100 g 80 159 10.8 28.4 38.0 7.8 ZrO₂~0.6 g Ga/100 g 81 157 14.4 36.3 39.7 7.0 ZrO₂ ~1.1 g Ga/100 g 82 15515.3 39.2 39.1 7.5 ZrO₂ ~2.2 g Ga/100 g 84 151 16.8 41.1 40.9 6.4 ZrO₂ToS = 72-96 hrs ~0.3 g Ga/100 g 80 159 10.5 27.3 38.4 7.0 ZrO₂ ~0.6 gGa/100 g 81 157 13.3 33.3 40.1 6.3 ZrO₂ ~1.1 g Ga/100 g 82 155 14.0 36.338.5 7.1 ZrO₂ ~2.2 g Ga/100 g 84 151 15.1 37.5 40.2 6.3 ZrO₂ Oxidecomponent Olefin present in Fraction in Selectivity SelectivitySelectivity Selectivity admixture [C₂-C₃ CH₄ C₄ Olefins C₄-C₅ ParaffinsCO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %] [C mol %] ToS =24-48 hrs ~0.3 g Ga/100 g 0.83 3.9 2.6 0.7 48.8 ZrO₂ ~0.6 g Ga/100 g0.85 1.5 2.9 0.6 50.0 ZrO₂ ~1.1 g Ga/100 g 0.84 2.4 2.7 0.8 49.3 ZrO₂~2.2 g Ga/100 g 0.86 1.4 2.7 0.8 49.6 ZrO₂ ToS = 72-96 hrs ~0.3 g Ga/100g 0.85 4.1 2.8 0.6 48.5 ZrO₂ ~0.6 g Ga/100 g 0.86 1.6 3.3 0.8 49.5 ZrO₂~1.1 g Ga/100 g 0.84 2.9 2.9 0.8 49.5 ZrO₂ ~2.2 g Ga/100 g 0.86 1.6 2.80.7 50.1 ZrO₂

Table 4b shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 3;temperature of 420° C.; pressure of 40 bar (4,000 kPa); and GHSV equals2400/h.

TABLE 4b Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~0.3 g Ga/100 g 106 225 21.8 52.4 41.6 13.3 ZrO₂~0.6 g Ga/100 g 101 221 24.3 60.9 39.8 15.5 ZrO₂ ~3.1 g Ga/100 g 130 17020.9 76.9 27.2 27.9 ZrO₂ ToS = 72-96 hrs ~0.3 g Ga/100 g 106 225 21.452.0 41.1 13.8 ZrO₂ ~0.6 g Ga/100 g 101 221 23.6 60.5 38.9 16.3 ZrO₂~3.1 g Ga/100 g 130 170 20.3 75.6 26.9 28.1 ZrO₂ Oxide component Olefinpresent in Fraction in Selectivity Selectivity Selectivity Selectivityadmixture [C₂-C₃ CH₄ C₄ Olefins C₄-C₅ Paraffins CO₂ with SAPO-34Product] [C mol %] [C mol %] [C mol %] [C mol %] ToS = 24-48 hrs ~0.3 gGa/100 g 0.76 1.1 3.8 1.3 38.9 ZrO₂ ~0.6 g Ga/100 g 0.72 1.1 4.0 1.438.2 ZrO₂ ~3.1 g Ga/100 g 0.49 1.2 5.7 2.5 35.6 ZrO₂ ToS = 72-96 hrs~0.3 g Ga/100 g 0.75 1.2 3.8 1.3 38.9 ZrO₂ ~0.6 g Ga/100 g 0.70 1.1 3.91.4 38.3 ZrO₂ ~3.1 g Ga/100 g 0.49 1.3 5.6 2.6 35.5 ZrO₂

Example 2 further demonstrates that Ga-deposited on monoclinic zirconiaenables very high olefin yields of composite catalysts in various syngasfeeds (2, 3) and process conditions. Very low loadings of Ga can enablean active material for monoclinic ZrO₂ of a high surface area.

Example 3

This example included composite catalysts with SAPO-34 as themicroporous catalyst component and featuring ZrO₂-supported galliumcatalysts (tetragonal-ZrO₂, BET surface area approximately 130 m²/g).The amounts of the sized 60-80 mesh mixed oxide particles used toprepare hybrid catalyst beds are reported in the Table 5a and 5b. Hybridcatalysts were prepared upon gentle shaking of particles together in avial.

Table 5a shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 2;temperature 390° C.; pressure 20 bar (2,000 kPa); and GHSV equals1200/h.

TABLE 5a Oxide component present in SAPO-34 Oxide Yield C₂-C₃Selectivity Selectivity admixture Weight Weight Olefins CO Conv. C₂-C₃Olefin C₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol%] [C mol %] ToS = 24-48 hrs ~0.3 g Ga/100 g 80 155 4.7 13.5 34.7 11.2ZrO₂ ~0.6 g Ga/100 g 80 153 7.1 17.0 41.8 8.7 ZrO₂ ~1.1 g Ga/100 g 81159 9.8 23.1 42.5 8.0 ZrO₂ ~2.2 g Ga/100 g 84 159 11.1 26.0 42.6 9.3ZrO₂ ToS = 72-96 hrs ~0.3 g Ga/100 g 80 155 4.5 12.4 36.8 10.2 ZrO₂ ~0.6g Ga/100 g 80 153 6.7 15.9 42.3 8.2 ZrO₂ ~1.1 g Ga/100 g 81 159 9.3 21.842.5 7.7 ZrO₂ ~2.2 g Ga/100 g 84 159 10.9 25.2 43.3 8.7 ZrO₂ Oxidecomponent Olefin present in Fraction in Selectivity SelectivitySelectivity Selectivity admixture [C₂-C₃ CH₄ C₄ Olefins C₄-C₅ ParaffinsCO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %] [C mol %] ToS =24-48 hrs ~0.3 g Ga/100 g 0.75 7.2 1.8 0.7 45.3 ZrO₂ ~0.6 g Ga/100 g0.83 3.1 2.1 0.6 45.2 ZrO₂ ~1.1 g Ga/100 g 0.84 2.9 2.0 0.7 45.4 ZrO₂~2.2 g Ga/100 g 0.82 2.3 2.0 0.8 45.0 ZrO₂ ToS = 72-96 hrs ~0.3 g Ga/100g 0.78 7.1 1.5 0.6 44.4 ZrO₂ ~0.6 g Ga/100 g 0.84 3.5 1.7 0.6 45.3 ZrO₂~1.1 g Ga/100 g 0.85 3.3 2.0 0.7 45.1 ZrO₂ ~2.2 g Ga/100 g 0.83 2.6 1.80.7 45.2 ZrO₂

Table 5b shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 3;temperature of 420° C.; pressure of 40 bar (4,000 kPa); and GHSV equals2400/h.

TABLE 5b Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~0.3 g Ga/100 g 100 226 7.6 19.6 38.6 24.0 ZrO₂~0.6 g Ga/100 g 106 239 11.8 28.4 41.6 19.4 ZrO₂ ~1.1 g Ga/100 g 109 20814.2 35.7 39.7 21.0 ZrO₂ ~2.2 g Ga/100 g 105 236 18.6 46.5 40.1 19.5ZrO₂ ToS = 72-96 hrs ~0.3 g Ga/100 g 100 226 6.7 17.9 37.4 26.5 ZrO₂~0.6 g Ga/100 g 106 239 10.4 25.7 40.5 21.6 ZrO₂ ~1.1 g Ga/100 g 109 20812.6 32.8 38.6 23.1 ZrO₂ ~2.2 g Ga/100 g 105 236 17.1 43.6 39.1 21.1ZrO₂ Oxide component Olefin present in Fraction in SelectivitySelectivity Selectivity admixture [C₂-C₃ CH₄ Selectivity C₄ OlefinsC₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %][C mol %] ToS = 24-48 hrs ~0.3 g Ga/100 g 0.62 1.5 3.8 1.5 30.6 ZrO₂~0.6 g Ga/100 g 0.68 1.3 3.6 1.4 32.7 ZrO₂ ~1.1 g Ga/100 g 0.65 1.3 3.61.5 33.1 ZrO₂ ~2.2 g Ga/100 g 0.67 1.2 3.8 1.5 33.7 ZrO₂ ToS = 72-96 hrs~0.3 g Ga/100 g 0.59 1.6 3.7 1.5 29.4 ZrO₂ ~0.6 g Ga/100 g 0.65 1.4 3.51.5 31.5 ZrO₂ ~1.1 g Ga/100 g 0.63 1.3 3.4 1.5 32.1 ZrO₂ ~2.2 g Ga/100 g0.65 1.3 3.7 1.6 33.1 ZrO₂

This example demonstrated that Ga-deposited on tetragonal zirconia is anactive component to catalyst composite (dual-particle bed). However,overall performance is inferior to Ga—ZrO₂ prepared on monoclinic-ZrO₂as for operations presented in Example 2.

Example 4

This example included hybrid catalysts featuring ZrO₂-supported galliummetal oxide catalyst components that also comprise other elements eitherin the zirconia carrier and/or co-impregnated with the galliumprecursor. In the first instance (Table 6a), zirconia carrier wasidentified as tetragonal zirconia that contained some lanthanum (La)(NORPRO, product no. SZ61156, containing approximately 7.3 g La per 100g ZrO₂). Gallium was impregnated onto this support either alone orco-impregnated with an additional amount of lanthanum. The latter caseis evidenced with an increased amount of La in the sample (the first vsthe second entry in the table). The amounts of the sized 60-80 meshmixed oxide particles used to prepare hybrid catalyst beds are reportedin the Table 6a. Hybrid catalysts were prepared upon gentle shaking ofparticles together in a vial.

Table 6a shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO=3; temperature of 390° C.;pressure 30 bar; and GHSV equals 1200/h.

TABLE 6a Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins CO Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~1.2 g Ga and 74 159 15.5 47.3 33.2 10.7 ~7.3 gLa/100 g ZrO₂ ~1.2 g Ga and 74 166 16.3 45.8 36.1 10.2 ~8.6 g La/100 gZrO₂ ToS = 72-96 hrs ~1.2 g Ga and 74 159 13.8 43.3 32.3 10.6 ~7.3 gLa/100 g ZrO₂ ~1.2 g Ga and 74 166 15.4 43.7 35.9 9.9 ~8.6 g La/100 gZrO₂ Oxide component Olefin present in Fraction in SelectivitySelectivity Selectivity Selectivity admixture [C₂-C₃ CH₄ C₄ OlefinsC₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol %] [C mol %] [C mol %][C mol %] ToS = 24-48 hrs ~1.2 g Ga and 0.76 2.8 7.9 1.3 45.2 ~7.3 gLa/100 g ZrO₂ ~1.2 g Ga and 0.78 2.7 7.4 1.1 44.2 ~8.6 g La/100 g ZrO₂ToS = 72-96 hrs ~ and 1.2 g Ga 0.75 3.6 7.9 1.0 45.8 ~7.3 g La/100 gZrO₂ ~1.2 g Ga and 0.78 3.1 7.3 1.0 44.5 ~8.6 g La/100 g ZrO₂

Table 6b shows the results a process for converting carbon oxide andcarbon dioxide (COx Conversion) into olefins with the following processconditions: H₂/CO/CO₂ equals 69.1/13.6/6.9 vol %; temperature of 390°C.; pressure 30 bar, GHSV equals 1200/h. Along the catalytic materialsreferenced in the Table 6a, the test further included additional samplesprepared on zirconia carrier identified as tetragonal zirconia thatcontained some tungsten (W) (NORPRO, product no. SZ61143, containsapproximately 11 wt % W). Ga-precursor was impregnated onto this supporteither alone or co-impregnated with La-precursor (third vs fourth entryin the Table 6b).

TABLE 6b Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Weight Weight C₂-C₃ Olefins COx Conv. C₂-C₃ OlefinC₂-C₃ Paraffin with SAPO-34 (mg) (mg) [C mol %] [C mol. %] [C mol %] [Cmol %] ToS = 24-48 hrs ~1.2 g Ga and 92 135 8.76 14.65 59.82 24.91 ~7.3g La/100 g ZrO₂ ~1.2 g Ga and 92 135 8.61 14.88 57.95 28.42 ~8.6 gLa/100 g ZrO₂ ~1.3 g Ga and 87 152 1.07 8.28 13.07 30.35 ~13.6 g W/100g  ZrO₂ ~1.2 g Ga and 90 156 0.87 8.46 10.19 53.92 ~1.2 g La and  13.6 gW/100 g ZrO₂ ToS = 72-96 hrs ~1.2 g Ga and 92 135 8.62 14.03 61.42 22.32~7.3 g La/100 g ZrO₂ ~1.2 g Ga and 92 135 8.62 14.33 60.35 25.32 ~8.6 gLa/100 g ZrO₂ ~1.3 g Ga and 87 152 0.98 8.09 12.24 27.76 ~13.6 g W/100g  ZrO₂ ~1.2 g Ga and 90 156 0.97 8.02 12.01 48.96 ~1.2 g La and  13.6 gW/100 g ZrO₂ Olefin Fraction in Selectivity Selectivity Selectivity[C₂-C₃ CH₄ C₄ Olefins C₄-C₅ Paraffins Product] [C mol %] [C mol %] [Cmol %] ToS = 24-48 hrs ~1.2 g Ga and 0.71 9.39 4.05 1.83 ~7.3 g La/100 gZrO₂ ~1.2 g Ga and 0.67 7.63 4.17 1.82 ~8.6 g La/100 g ZrO₂ ~1.3 g Gaand 0.3 53.65 0.17 2.75 ~13.6 g W/100 g  ZrO₂ ~1.2 g Ga and 0.16 25.422.1 8.36 ~1.2 g La and  13.6 g W/100 g ZrO₂ ToS = 72-96 hrs ~1.2 g Gaand 0.73 10.72 3.74 1.79 ~7.3 g La/100 g ZrO₂ ~1.2 g Ga and 0.7 8.47 3.52.35 ~8.6 g La/100 g ZrO₂ ~1.3 g Ga and 0.31 57.55 0 2.46 ~13.6 g W/100g  ZrO₂ ~1.2 g Ga and 0.2 28.8 2.12 8.11 ~1.2 g La and  13.6 g W/100 gZrO₂

Example 4 demonstrates that Ga-deposited on tetragonal zirconia with Lain the support is an active and stable composite catalyst. In contrast,tetragonal zirconia with W present significantly impairs its catalyticbehavior. Co-impregnated La can mitigate some adverse effects ofW-present (i.e., an effect on methane selectivity).

Example 5

This example included catalysts with SAPO-34 microporous catalystcomponents and featuring ZrO₂-supported gallium/lanthanum catalyst. Ascarrier to prepare the latter a commercial sample of monoclinic-ZrO₂ wasused (NORPRO product no. SZ31108, BET surface area approximately 70m²/g). The catalyst was tested in a long process run across variedprocess conditions.

Table 7a shows the results for converting syngas into olefins for onehybrid catalyst in a process study during which process conditions werechanged in time of the process. The hybrid catalyst was prepared from123 mg of SAPO-34 component and 185 mg of the mixed Ga—La/ZrO₂ mixedoxide component upon gentle shaking of sized particles 60-80 mesh ofboth components together in a vial. The average catalytic results arereported for each process segment and include start and finish of eachprocess segment (Min ToS [hrs]−Max ToS [hrs]) Note, that time-on-streamwas counted from the onset of the exposure to syngas. Each processsegment had different process operations parameters like H₂/CO ratio andspace velocity while, the temperature and pressure of the process werekept constant.

TABLE 7a Oxide component present in SAPO-34 Oxide Min Max admixtureWeight Weight ToS ToS SP GHSV P T with SAPO-34 (mg) (mg) [hrs] [hrs]SYNGAS [h−1] [bar] [° C.] ~2.2 g Ga and 123 185 108.1 143.9 2.9 1800.040.0 400.0 1.45 g La/100 g 146.6 184.5 2.9 2400.0 40.0 400.0 ZrO₂ 187.3225.3 3.2 1200.0 40.0 400.0 Yield Selectivity Selectivity OlefinSelectivity C₂-C₃ CO C₂-C₃ C₂-C₃ Fraction in Selectivity SelectivityC₄-C₅ Selectivity Olefins Conv. Olefin Paraffin [C₂-C₃ CH₄ C₄ OlefinsParaffins CO₂ [C mol %] [C mol. %] [C mol %] [C mol %] Product] [C mol%] [C mol %] [C mol %] [C mol %] 20.8 66.6 31.3 20.6 0.60 1.1 8.8 2.435.8 19.9 59.7 33.4 18.1 0.65 1.1 8.4 2.3 36.8 18.7 75.1 25.0 27.6 0.471.2 9.4 2.8 34.0

Table 7b shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 3;temperature of 390 to 400° C.; pressure equals 30 bar; and GHSV equals1200/h to 2400/h.

Table 7b shows the results for converting syngas into olefins for hybridcatalyst in a long process study where process conditions were changedin time of the process. The hybrid catalyst was prepared from 147 mg ofSAPO-34 component and 130 mg of the mixed Ga—La/ZrO₂ mixed oxidecomponent upon gentle shaking of sized particles 60-80 mesh of bothcomponents together in a vial. The average catalytic results arereported for each process segment and include start and finish of eachprocess segment (Min ToS [hrs]−Max ToS [hrs]) Note, that time-on-streamwas counted from the onset of the exposure to syngas. Each processsegment had different process operations parameters like H₂/CO ratio,space velocity or temperature, while pressure of the process was keptconstant (30 bars).

TABLE 7b Oxide component present in SAPO-34 Oxide Min Max admixtureWeight Weight ToS ToS SP GHSV P T with SAPO-34 (mg) (mg) [hrs] [hrs]SYNGAS [h⁻¹] [bar] [° C.] ~2.2 g Ga and 147 130 110.7 163.8 3.0 1800.030.0 390.0 1.45 g La/100 g 166.9 220.0 3.0 2400.0 30.0 390.0 ZrO₂ 223.1276.4 3.3 1200.0 30.0 390.0 279.5 298.5 3.3 1200.0 30.0 395.0 301.6326.0 3.3 1200.0 30.0 400.0 Yield Selectivity Selectivity OlefinSelectivity C₂-C₃ CO C₂-C₃ C₂-C₃ Fraction Selectivity Selectivity C₄-C₅Selectivity Olefins Conv. Olefin Paraffin in [C₂-C₃ CH₄ C₄ OlefinsParaffins CO₂ [C mol %] [C mol. %] [C mol %] [C mol %] Product] [C mol%] [C mol %] [C mol %] [C mol %] 18.5 47.7 38.7 16.5 0.70 1.0 4.8 1.737.2 16.4 42.5 38.7 15.6 0.71 1.1 4.8 1.7 37.8 20.2 56.8 35.5 20.1 0.641.0 5.4 1.8 36.1 21.0 59.7 35.2 20.8 0.63 1.0 5.3 1.7 35.9 21.1 62.733.6 22.9 0.59 1.1 5.4 1.8 35.3

Example 5 demonstrates that Ga/La—ZrO₂ can sustain syngas to olefinprocess over prolonged times and in high yield in olefins across variousprocess (p, T, GHSV) conditions.

Example 6

This example included hybrid catalysts with SAPO-34 microporous catalystcomponents featuring Ga—ZrO₂ metal oxide catalyst component. It comparesa semi-crystalline co-precipitated mixed oxide Ga—ZrO₂ (a syntheticmethodology alternative to impregnation) where an intimatejunction-Ga—ZrO₂ may exist but ZrO₂ shows poor crystallinity effectivelyrendering an inferior catalytic system. It also compares Ga—ZrO₂prepared via slurry-processing & calcination of crystallinemonoclinic-ZrO₂ and a Ga-precursor in a form of Ga₂O₃ (a syntheticmethodology alternative to impregnation) where crystalline powdersproduce the desired catalytic effect. Furthermore it compares to aphysical mixture of powders without any processing to create an intimatejunction of Ga₂O₃ and ZrO₂ where the hybrid system with SAPO-34 shows anunderdeveloped catalytic performance. The amounts of the sized 60-80mesh mixed oxide particles used to prepare hybrid catalyst beds arereported in the Table 8a. Hybrid catalysts were prepared upon gentleshaking of particles together in a vial.

Table 8a shows the results a process for converting syngas into olefinswith the following process conditions: H₂/CO approximately 3;temperature of 420° C.; pressure equals 40 bar (4,000 kPa); and GHSVequals 2400/h.

TABLE 8a Oxide component present in SAPO-34 Oxide Yield SelectivitySelectivity admixture Preparation/ Weight Weight C₂-C₃ Olefins CO Conv.C₂-C₃ Olefin C₂-C₃ Paraffin with SAPO-34 comments (mg) (mg) [C mol %] [Cmol. %] [C mol %] [C mol %] ToS = 24-48 hrs ~13.2 g Ga/100 gCo-precipitation/ 111 78 1.3 16.8 7.5 36.5 ZrO₂ lacks crystalline ZrO₂ ~1.7 g Ga/100 g slurry-processing/ 102 181 15.4 40.0 38.6 17.9 ZrO₂crystalline ZrO₂ ~14.0 g Ga/100 g Slurry-processing/ 99 180 19.5 51.737.7 18.5 ZrO₂ crystalline ZrO₂ ~41.7 g Ga/100 g Slurry-processing/ 104181 12.8 47.0 27.3 28.5 ZrO₂ crystalline ZrO₂ ~2.72 g Ga/100 g drypowder mix/ 99 181 6.1 25.4 23.9 29.2 ZrO₂ crystalline ZrO₂ ~20.4 gGa/100 g dry powder mix/ 103 187 9.0 36.3 24.9 29.3 ZrO₂ crystallineZrO₂ ToS = 72-96 hrs ~13.2 g Ga/100 g Co-precipitation/ 111 78 1.2 14.78.4 34.3 ZrO₂ lacks crystalline ZrO₂  ~1.7 g Ga/100 g slurry-processing/102 181 15.5 40.8 37.9 18.3 ZrO₂ crystalline ZrO₂ ~14.0 g Ga/100 gSlurry-processing/ 99 180 19.3 51.5 37.5 18.3 ZrO₂ crystalline ZrO₂~41.7 g Ga/100 g Slurry-processing/ 104 181 12.2 45.6 26.8 28.6 ZrO₂crystalline ZrO₂ ~2.72 g Ga/100 g dry powder mix/ 99 181 6.4 27.2 23.529.2 ZrO₂ crystalline ZrO₂ ~20.4 g Ga/100 g dry powder mix/ 103 187 9.036.7 24.5 29.4 ZrO₂ crystalline ZrO₂ Oxide component Olefin present inFraction in Selectivity Selectivity Selectivity Selectivity admixture[C₂-C₃ CH₄ C₄ Olefins C₄-C₅ Paraffins CO₂ with SAPO-34 Product] [C mol%] [C mol %] [C mol %] [C mol %] ToS = 24-48 hrs ~13.2 g Ga/100 g 0.176.5 1.4 8.3 39.5 ZrO₂  ~1.7 g Ga/100 g 0.68 1.3 1.8 1.5 39.0 ZrO₂ ~14.0g Ga/100 g 0.67 1.6 1.7 2.2 38.2 ZrO₂ ~41.7 g Ga/100 g 0.49 1.9 1.6 3.237.6 ZrO₂ ~2.72 g Ga/100 g 0.45 2.6 1.7 2.4 40.2 ZrO₂ ~20.4 g Ga/100 g0.46 2.3 1.8 2.8 38.9 ZrO₂ ToS = 72-96 hrs ~13.2 g Ga/100 g 0.20 8.3 1.48.0 39.6 ZrO₂  ~1.7 g Ga/100 g 0.67 1.4 1.8 1.5 39.1 ZrO₂ ~14.0 g Ga/100g 0.67 1.8 1.7 2.3 38.3 ZrO₂ ~41.7 g Ga/100 g 0.48 2.1 1.6 3.3 37.6 ZrO₂~2.72 g Ga/100 g 0.45 2.8 1.8 2.6 40.1 ZrO₂ ~20.4 g Ga/100 g 0.45 2.51.8 2.8 38.9 ZrO₂

Example 6 demonstrated that Ga—ZrO₂ can be created with differenttechnologies of preparation; however, care must be taken to ensure ZrO₂is delivered in a well crystalline form such as monoclinic polymorph.Methods for obtaining a very active component Ga—ZrO₂ to dual-particlecatalyst bed with SAPO-34 appears to be impregnation (Examples 1-5).However, upon certain process operations physical mixtures of ZrO₂ andGa₂O₃ may also gain activity with prolonged process exposure affectingre-distribution of elements in presence of reactants and product gases.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the embodiments describedherein without departing from the spirit and scope of the claimedsubject matter. Thus it is intended that the specification cover themodifications and variations of the various embodiments described hereinprovided such modification and variations come within the scope of theappended claims and their equivalents.

1. A process for preparing C₂ to C₄ olefins comprising: introducing afeed stream comprising hydrogen gas and a carbon-containing gas selectedfrom the group consisting of carbon monoxide, carbon dioxide, andmixtures thereof into a reaction zone of a reactor; and converting thefeed stream into a product stream comprising C₂ to C₄ olefins in thereaction zone in the presence of a hybrid catalyst, the hybrid catalystcomprising: a metal oxide catalyst component comprising gallium oxideand phase pure zirconia; and a microporous catalyst component.
 2. Theprocess of claim 1, wherein the phase pure zirconia comprisescrystalline phase pure zirconia.
 3. The process of claim 1, wherein thephase pure zirconia comprises monoclinic phase pure zirconia.
 4. Theprocess of claim 1, wherein the phase pure zirconia has a BET surfacearea that is greater than or equal to 40 m²/g.
 5. The process of claim1, wherein the phase pure zirconia has a BET surface area that isgreater than or equal to 100 m²/g.
 6. The process of claim 1, whereinthe metal oxide catalyst component comprises from greater than 0.0 ggallium per 100 g phase pure zirconia to 30.0 g gallium per 100 g ofphase pure zirconia.
 7. The process of claim 1, wherein the metal oxidecatalyst component comprises from greater than 0.0 g gallium per 100 gphase pure zirconia to 15.0 g gallium per 100 g of phase pure zirconia.8. The process of claim 1, wherein microporous catalyst componentcomprises an 8 membered ring structure.
 9. The process of claim 1,wherein the microporous catalyst component comprises SAPO-34.
 10. Theprocess of claim 1, wherein the metal oxide catalyst component comprisesfrom 1.0 wt % to 99.0 wt % of the hybrid catalyst.
 11. The process ofclaim 1, wherein the metal oxide catalyst component comprises from 60.0wt % to 90.0 wt % of the hybrid catalyst.
 12. The process of claim 1,wherein a temperature within the reaction zone during the converting isfrom 350° C. to 450° C.
 13. The process of claim 1, wherein a pressurewithin the reaction zone during the converting is at least 1 bar (100kPa).
 14. The process of claim 1, wherein a GHSV within the reactionzone during the converting is from 1,200/h to 12,000/h.
 15. The processof claim 1, wherein the metal oxide catalyst component is formed by animpregnation method.
 16. The process of claim 1, wherein: the phase purezirconia comprises crystalline phase pure zirconia; the metal oxidecatalyst component comprises from greater than 0.0 g gallium per 100 gphase pure zirconia to 30.0 g gallium per 100 g of phase pure zirconia;and the microporous catalyst component comprises SAPO-34.
 17. Theprocess of claim 1, wherein: a temperature within the reaction zoneduring the converting is from 350° C. to 450° C.; a pressure within thereaction zone during the converting is at least 1 bar (100 kPa); and aGHSV within the reaction zone during the converting is from 1,200/h to12,000/h.